Dichloro methyl sulfenyl chloride



2,484,06 DIOHL BO METHY SUL CHL RIDE Sylvan R. Wood, Stiliwater, Okla assignor to Cities Service Oil Company, Bartiesvillc, Okla, a corporation of Delaware No Dra- Application May 22, 1948, Serial No. 28,751 2 Claims. (Cl. 260-543) 2 This invention relates to chlorinated organic the product may be removed by bubblin an inert compounds and more ar icularly to diehloro a thmu t, methyl sulfeuyl chloride, a new composition of The yield of crude product on four runs avermatten aged slightly over 94 per cent with amounts of I hav covered the. dichloro methyl sulienyl 5 trithiane varying fr five to fifteen g being chloride made be prepared by ting trithiane ed. conversion appears to be practically in state with c rine hich has been quantitativ Individual yields varied from a out previously driedby a onvenient method such as 92.5 per ce 0 as high as about 95.1 per cent by passing it throug tower containing con- The difference between these figures and 100 per centmted s lf ric lo cent is no oubt due to the occurrence of a sec- The trithiane d by me was prepa ed in the ondary reaction. usual mantle by passing drogen sulfide gas number of such preparations were made with into a com ercial forma solution to hich con quantitative measurements of the reactants and centrated hydroc oric acid had been added sufthe reaction products from which the iollowlng ficient to ma e a '10 per cent acid solution. S summa is typicalfuric aci con i d to be ually .eilicient Grams m catalyzing the reaction which proceeds accord- W eight of trithiane 4.92 ing to the following equation. Weight of chlorine 14.83 Weight of chlorine co bined 10.04 acid 3H 0 Weight of produc 14.96 33030 31% Q Weight of chlorine uncombined 4.19 8-0 a Weight of hydrogen chlorine found 4.32 T Tillman after an Period 9 Thus six mols of chlorine were consumed in conabollt 811mm! Separate-5 mtg of char verting one moi of trithiane into three mols of aoteristic OdOY- 5 15 mt Ted away the dichloro methyl sulienyl chloride and three mols mother liq Washed free {mm rides and of hydrogen chloride. The trithiane molecule dri d. e P 05 h memng apparently splits in three equal pa with each h rp at 21 d the Yield 15 P many (CHrgroup adding three atoms of chlorine u n while splitting out one atom of drogen as by A n 6111? quantity 0 mtmane prepared drogen chloride, which is vaporized om the sysas a v 1 P191; in fitted with mm an tern. The sulfenyl chloride is a yellowish re inlet and n tube- Dry cmwme gas fuming liquid with an odor resembling the s 815586 in at moderate m the surface fur chlorides. Its important p sical and chemof h tfltmane iew mutes the forum" ical properties h ve been dete ined as follows tion of a y red liquidm y be observed, the

ount of ii uid increas apidly until the o ar wgsht. t m id trithiane compl tely disappeared. The BY he 1mm g m liquid efferves oticeabiy through lit the 18- benzene action, t by hloric acid ved being car- Themem 1 fled n through t e outlet tub he-reaction Density 15143340 m m tne an t be controlled by Refractive index 1-5428/34 mmmn 8 reaction fl sk 1 W409 Sp ifi r fl ivi .194! t r sine if the temperature allowed to rise Molecular refmmvm' 2939 too a secondary reaction sets which w Molecular reilactivity, theoretical reduce the yield oi dichloro methyl sullen? The chemical composition was determined by chloride. repeated analyses for chlorine and sulfur content: When evolution-oi hydrochloric acid has finally P e t ceased, e reactio mplete. a s Cm n v m er 0 n sample of tritlriiane for instanceif rgiiinsay 19 to 15 gai e I10 0 09 the conversi n is comp e rom onehalf to three-quarters of an hour. The time may 'g iz f CIHHMI -25 be shortened by re ovalafirom the dcooling 1gia'rih 32 23 o 21 1 t frequen intervals ow a mo era e r e n tempera e, but, s been at ted above, he Theoretical f r Clr-CFL-SCl 21.15 temperat should n be allow to rise su 55 In order to determine the activity of the chlostantially, otherwise ondary eaction wil e atoms the com und, a we h d sample take pie The product appears as a yellowis of the compou d dissolved in alcohol was eate ed mobil liqui witha greeable odor strongly with alcoholic potassi hydroxide until active resembling that of sulfur mon chloride. races chlorine was ompletely precipitated potasof chlorine and c oric re in W sium chloride which was flitere washed with .pound has the structural formul b 3 benzene, dried and dissolved in distilled water. Chloride was then determined both volumetricaliy and gravimetrically. The gravimetric equivalents of active chlorine per mol were 1.93 and the volumetric equivalents of active chlorine per mol l was 2.00.

F om this data it is evident that the compound has two readily replaceable chlorine atoms.

to the class of compoun fenyl halides in which a halogen atom is attached to sulfur, the sulfur in turn carbon. The h compound, especially tan properties. From its close resemblance to $111- fur monochloride it is indicated that the com- The product reactswith olefins by addition,

with the active halogen of the. sulfenyl chloride us cyclohexene reacts readily 30 Remboidt 4 with the sulfenyl chloride forming a dark oily Product with combined chlorine and sulfur.

My new product, dichloro methyl sulfenyl chloas an intere method of synthesizing dichloro methyl sulfenyl chloride comprising reacting dry trithiane with dry chlorine gas until the reaction is complete. SYLVAN' R. WOOD.-

REFERENCES CITED The following references are ofrecord i the this patent:

m sm'rns PATENTS Klason, Berichte. vol. 20, pp. 23772378 (1887)., DP. 657480 et al., Berichte, vol. 723 

